Biomass conversion process to hydrocarbons

ABSTRACT

A process for the production of a higher hydrocarbon useful to produce diesel components from solid biomass is provided. The process provides for improved production of diesel components by contacting the stable oxygenated hydrocarbon intermediate containing diols produced from digestion and hydrodoxygenation of the solid biomass to an amorphous silica alumina catalyst to reduce the diols content, and removing water prior to contacting with the condensation catalyst to produce the higher hydrocarbon.

The present application claims the benefit of U.S. ProvisionalApplication Ser. No. 62/186,960, filed 30 Jun. 2015, the entiredisclosure of which is hereby incorporated by reference.

FIELD OF THE INVENTION

The invention relates to conversion of biomass to hydrocarbons. Morespecifically, the invention relates to improved production of higherhydrocarbons useful as liquid biofuels from solid biomass.

BACKGROUND OF THE INVENTION

A significant amount of attention has been placed on developing newtechnologies for providing energy from resources other than fossilfuels. Biomass is a resource that shows promise as a fossil fuelalternative. As opposed to fossil fuel, biomass is also renewable.

Biomass may be useful as a source of renewable fuels. One type ofbiomass is plant biomass. Plant biomass is the most abundant source ofcarbohydrate in the world due to the lignocellulosic materials composingthe cell walls in higher plants. Plant cell walls are divided into twosections, primary cell walls and secondary cell walls. The primary cellwall provides structure for expanding cells and is composed of threemajor polysaccharides (cellulose, pectin, and hemicellulose) and onegroup of glycoproteins. The secondary cell wall, which is produced afterthe cell has finished growing, also contains polysaccharides and isstrengthened through polymeric lignin covalently cross-linked tohemicellulose. Hemicellulose and pectin are typically found inabundance, but cellulose is the predominant polysaccharide and the mostabundant source of carbohydrates. However, production of fuel fromcellulose poses a difficult technical problem. Some of the factors forthis difficulty are the physical density of lignocelluloses (like wood)that can make penetration of the biomass structure of lignocelluloseswith chemicals difficult and the chemical complexity of lignocellulosesthat lead to difficulty in breaking down the long chain polymericstructure of cellulose into carbohydrates that can be used to producefuel. Another factor for this difficulty is the nitrogen compounds andsulfur compounds contained in the biomass. The nitrogen and sulfurcompounds contained in the biomass can poison catalysts used insubsequent processing.

Most transportation vehicles require high power density provided byinternal combustion and/or propulsion engines. These engines requireclean burning fuels which are generally in liquid form or, to a lesserextent, compressed gases. Liquid fuels are more portable due to theirhigh energy density and their ability to be pumped, which makes handlingeasier.

Currently, bio-based feedstocks such as biomass provide the onlyrenewable alternative for liquid transportation fuel. Unfortunately, theprogress in developing new technologies for producing liquid biofuelshas been slow in developing, especially for liquid fuel products thatfit within the current infrastructure. Although a variety of fuels canbe produced from biomass resources, such as ethanol, methanol, andvegetable oil, and gaseous fuels, such as hydrogen and methane, thesefuels require either new distribution technologies and/or combustiontechnologies appropriate for their characteristics. The production ofsome of these fuels also tends to be expensive and raise questions withrespect to their net carbon savings. There is a need to directly processbiomass into liquid fuels, amenable to existing infrastructure.

Processing of biomass as feeds is challenged by the need to directlycouple biomass hydrolysis to release sugars, and catalytichydrogenation/hydrogenolysis/hydrodeoxygenation of the sugar, to preventdecomposition to heavy ends (caramel, or tars). Further, it is achallenge to minimize generation of waste products that may requiretreating before disposal and/or catalyst deactivation by poisons.

SUMMARY OF THE INVENTION

It was found that glycols in the oxygenated hydrocarbon intermediateproduced by digesting and hydrodeoxygenating solid biomass in a liquiddigestive solvent tend to rapidly coke the condensation catalyst in thesubsequent condensation reaction that produces higher hydrocarbons.Applicants have found that by contacting the oxygenated hydrocarbonintermediate with an acidic silica alumina catalyst under certainreaction conditions producing monooxygenated stream prior tocondensation reaction provides processing advantages. These advantagesinclude at least one of extending the life of catalysts used insubsequent processing steps, producing components valuable as liquidbiofuels, and providing a readily separable solvent for use inproduction of biofuels.

In one embodiment, a process for the production of a higher hydrocarbonfrom solid biomass, said process comprising:

-   -   a. providing a biomass solid containing cellulose,        hemicellulose, and lignin;    -   b. digesting and hydrodeoxygenating the biomass solid in a        liquid digestive solvent, said digestive solvent containing a        solvent mixture having a boiling point of greater than 40° C. in        the presence of a hydrothermal hydrocatalytic in the presence of        hydrogen at a temperature in the range of 110° C. to less than        300° C. at a pressure in a range of from 20 bar to 200 bar to        form a stable oxygenated hydrocarbon intermediate product having        a viscosity of less than 100 centipoise (at 50° C.), a diol        content of at least 2 wt. %, less than 2 wt % of sugar, and less        than 2 wt % acid (acetic acid equivalent) based on the        intermediate product, and at least 60% of carbon exists at less        than or equal to 9;    -   c. reacting at least a portion of the stable oxygenated        hydrocarbon intermediate product with an acidic amorphous silica        alumina catalyst at a temperature in the range from 300° C. to        400° C. thereby producing monooxygenated stream containing water        and monooxygenates having a boiling point of at least 40° C.;    -   d. condensing the monooxygenated stream to liquid phase        producing an aqueous phase and an organic phase;    -   e. removing at least a portion of aqueous phase from the organic        phase to provide a condensed organic stream containing the        monooxygenates;    -   f. contacting the monooxygenates having boiling point of at        least 40° C. in the condensed organic stream with a strong        acidic solid catalyst at a temperature in the range from 300° C.        to about 350° C. and a pressure in a range from 500 to 1200 psi        producing a higher hydrocarbons stream containing unsaturated        hydrocarbons including olefins and dienes.

The features and advantages of the invention will be apparent to thoseskilled in the art. While numerous changes may be made by those skilledin the art, such changes are within the spirit of the invention.

BRIEF DESCRIPTION OF THE DRAWING

The drawings illustrate certain aspects of some of the embodiments ofthe invention, and should not be used to limit or define the invention.

FIG. 1 is a schematic illustration of an embodiment of a process of thisinvention.

FIG. 2 is a GC trace of an oxygenated hydrocarbon intermediate productfrom Example 10.

FIG. 3 is a GC trace of an organic layer from the monooxygenated streamfrom Example 12.

FIG. 4 is a gas chromatograph of a diesel produced according to Example14.

FIG. 5 is a gas chromatography of a commercial no. 2 standard diesel.

DETAILED DESCRIPTION OF THE INVENTION

In one embodiment, the invention relates to contacting the oxygenatedhydrocarbon intermediate, produced from digesting and hydrodeoxygenatinga solid biomass in a liquid digestive solvent, with an acidic silicaalumina catalyst under certain reaction conditions producingmonooxygenated stream prior to condensation reaction. It has been foundthat the acidic silica alumina catalyst treatment prior to thecondensation reaction extends the catalyst life of the condensationcatalyst. In another aspect, the process provides means to readilyseparate an organic phase from an aqueous phase, which at least aportion of the organic phase can be recycled to be used as a digestivesolvent.

The higher hydrocarbons produced are useful in forming diesel fuel. Asused herein, the term “higher hydrocarbons” refers to hydrocarbonshaving an oxygen to carbon ratio less than the oxygen to carbon ratio ofat least one component of the biomass feedstock. The higher hydrocarbonpredominantly contains C4 to C30 hydrocarbons, more preferably C6 to C18hydrocarbons. As used herein the term “hydrocarbon” refers to an organiccompound comprising primarily hydrogen and carbon atoms, which is alsoan unsubstituted hydrocarbon. In certain embodiments, the hydrocarbonsof the invention also comprise heteroatoms (i.e., oxygen sulfur,phosphorus, or nitrogen) and thus the term “hydrocarbon” may alsoinclude substituted hydrocarbons. As used herein, the term “solublecarbohydrates” refers to monosaccharides or polysaccharides that becomesolubilized in a digestion process. Although the underlying chemistry isunderstood behind digesting cellulose and other complex carbohydratesand further transforming simple carbohydrates into organic compoundsreminiscent of those present in fossil fuels, high-yield andenergy-efficient processes suitable for converting cellulosic biomassinto fuel blends have yet to be developed. In this regard, the mostbasic requirement associated with converting cellulosic biomass intofuel blends using digestion and other processes is that the energy inputneeded to bring about the conversion should not be greater than theavailable energy output of the product fuel blends. Further the processshould maximize product yield while minimizing waste products. Thesebasic requirements lead to a number of secondary issues thatcollectively present an immense engineering challenge that has not beensolved heretofore.

In a method of production of hydrocarbons, pyrolysis of biomass has beenreported. Pyrolysis is the thermal decomposition of biomass occurring inthe absence of oxygen. The products of biomass pyrolysis includebiochar, bio-oil and gases including methane, hydrogen, carbon monoxide,and carbon dioxide. Depending on the thermal environment and the finaltemperature, pyrolysis will yield mainly biochar at low temperatures,less than 450° C., when the heating rate is quite slow, and mainly gasesat high temperatures, greater than 800° C., with rapid heating rates. Atan intermediate temperature and under relatively high heating rates, themain product is bio-oil. Pyrolysis products can be upgraded to fuel suchas disclosed in U.S. Pat. No. 8,143,464. However, such process producesa large quantity of biochar and gases such as methane, hydrogen, carbonmonoxide, and carbon dioxide.

Unlike a pyrolysis process, digestion and hydrocatalytichydrodeoxygenation produces a liquid oxygenated hydrocarbon intermediatewith minimal biochar or gaseous carbon monoxide and carbon dioxides.However, under the milder conditions that produce the oxygenatedhydrocarbon intermediates also forms glycols that tend to coke thecondensation catalyst to produce the higher hydrocarbons.

Processing of biomass as feeds is challenged by the need to directlycouple biomass hydrolysis to release sugars, and catalytichydrogenation/hydrogenolysis/hydrodeoxygenation of the sugar, to preventdecomposition to heavy ends (caramel, or tars). It was found thatglycols in the oxygenated hydrocarbon intermediate produced by digestingand catalytically hydrodeoxygenating solid biomass in a liquid digestivesolvent tend to rapidly coke the condensation catalyst in the subsequentcondensation reaction that produces higher hydrocarbons. It was foundthat contacting (and reacting) the oxygenated hydrocarbon intermediatecontaining diols with an acidic amorphous silica alumina catalyst at atemperature in the range of 300° C. to 400° C. producing monooxygenatedstream prior to condensation reaction can reduce coke formation on thecatalyst during condensation reaction.

It has further been found that when the monooxygenated stream iscondensed to liquid phase, water can be effectively removed from theprocess by phase separation, further protecting the condensationcatalyst from degradation. Upon condensation, the monooxygenated streamreadily separates into an aqueous phase containing water and an organicphase containing the monooxygenates. At least a portion of the organicphase may be recycled to be used as digestive solvent.

Various illustrative embodiments will be further described withreference to FIG. 1. In FIG. 1 show illustrative embodiments of biomassconversion process to hydrocarbon.

Any suitable (e.g., inexpensive and/or readily available) type oflignocellulosic biomass can be used as a solid biomass. Suitablelignocellulosic biomass can be, for example, selected from, but notlimited to, wood, forestry residues, agricultural residues, herbaceousmaterial, municipal solid wastes, pulp and paper mill residues, andcombinations thereof. Thus, in some embodiments, the biomass cancomprise, for example, corn stover, straw, bagasse, miscanthus, sorghumresidue, switch grass, duckweed, bamboo, water hyacinth, hardwood,hardwood chips, hardwood pulp, softwood, softwood chips, softwood pulp,and/or combination of these feedstocks. The biomass can be chosen basedupon a consideration such as, but not limited to, cellulose and/orhemicelluloses content, lignin content, growing time/season, growinglocation/transportation cost, growing costs, harvesting costs and thelike.

Prior to processing, the untreated biomass can be reduced in size (e.g.,chopping, crushing or debarking) to a convenient size and certainquality that aids in moving the biomass or mixing and impregnating thechemicals from digestive solvent. Thus, in some embodiments, providingbiomass can comprise harvesting a lignocelluloses-containing plant suchas, for example, a hardwood or softwood tree. The tree can be subjectedto debarking, chopping to wood chips of desirable thickness, and washingto remove any residual soil, dirt and the like.

The biomass solids are introduced in to a vessel from an inlet. Thevessel can be in any shape that include, for example, vertical,horizontal, incline, and may include bends, curves or u shape. Thevessel will further have at least one inlet and at least one outlet.

The biomass may optionally be washed with an acidic or basic solution toremove metal species and its corresponding anions such as Mg, Ca, Na, KFe, Mn, Cl, SO₄, PO₄, NO₃ that are detrimental to catalysts or equipmentused in the hydrothermal hydrocatalytic treatment from the biomass. Suchtreatment disclosed in commonly owned U.S. Patent Application Nos.61/917,382, 61/917,400, 61/917,406, 61/917,414, 61/917,393, 61/917,402,61/917,419, 61/917,422, 61/917,445, and 61/917,448 filed Dec. 18, 2013,which disclosures are hereby incorporated by reference in its entirety.

At least a portion of the optionally treated cellulosic biomass solidsis provided to a digestion and/or reaction zone (collectively referredto as “hydrothermal hydrocatalytic reaction zone” 10) for digesting andhydrodeoxygenating. This zone may be conducted in a single step or inmultiple steps or vessels as described below.

For the hydrothermal catalytic reaction zone, the zone may have one ormore vessels. In one embodiment in the digestion/reaction zonehydrolysis and hydrothermal hydrocatalytic reaction of the treatedbiomass is carried out in one or more vessels. These vessels may bedigesters or reactors or combination thereof including a combinationhydrothermal hydrocatalytic digestion unit.

In some embodiments, lignocellulosic biomass (solids), 2 beingcontinuously or semi-continuously added to the hydrothermal digestionunit or hydrothermal hydrocatalytic digestion unit may be pressurizedbefore being added to the unit, particularly when the hydrothermal(hydrocatalytic) digestion unit is in a pressurized state.Pressurization of the cellulosic biomass solids from atmosphericpressure to a pressurized state may take place in one or morepressurization zones before addition of the cellulosic biomass solids tothe hydrothermal (hydrocatalytic) digestion unit. Suitablepressurization zones that may be used for pressurizing and introducinglignocellulosic biomass to a pressurized hydrothermal digestion unit orhydrothermal hydrocatalytic digestion unit are described in more detailin commonly owned U.S. Patent Application Publication Nos. US20130152457and US20130152458, and incorporated herein by reference in its entirety.Suitable pressurization zones described therein may include, forexample, pressure vessels, pressurized screw feeders, and the like. Insome embodiments, multiple pressurization zones may be connected inseries to increase the pressure of the cellulosic biomass solids in astepwise manner. The digestion and the hydrothermal hydrocatalyticreaction in the hydrothermal catalytic reaction zone (or digestionreaction zone) may be conducted separately, partially combined, or insitu.

The biomass solid is hydrothermally digested and hydrodeoxygenated in aliquid-phase digestive solvent, in the presence of hydrogen and acatalyst capable of activating molecular hydrogen (hydrothermalhydrocatalytic catalyst), at a temperature in the range of from 110° C.to less than 300° C. at a pressure in a range of from 20 bar to 200 barto form stable oxygenated hydrocarbon intermediate product mixtures. Thestable oxygenated hydrocarbon intermediate product mixture, in general,has a viscosity of less than 100 centipoise (at 50° C.), a diol contentof at least 2 wt. % of diols, less than 2 wt. % of sugar, and less than2 wt. % organic acid based on acetic acid equivalent, and at least 60%of carbon in formed product exists in molecules having 10 carbon atomsor less.

In some embodiments, the digestion rate of cellulosic biomass solids maybe accelerated in the presence of a liquid phase containing a digestionsolvent. In some instances, the liquid phase may be maintained atelevated pressures that keep the digestion solvent in a liquid statewhen raised above its normal boiling point. Although the more rapiddigestion rate of cellulosic biomass solids under elevated temperatureand pressure conditions may be desirable from a throughput standpoint,soluble carbohydrates may be susceptible to degradation at elevatedtemperatures. One approach for addressing the degradation of solublecarbohydrates during hydrothermal digestion is to conduct an in situcatalytic reduction reaction process so as to convert the solublecarbohydrates into more stable compounds as soon as possible after theirformation.

In certain embodiments, a slurry catalyst may be effectively distributedfrom the bottom of a charge of cellulosic biomass solids to the topusing upwardly directed fluid flow to fluidize and upwardly conveyslurry catalyst particulates into the interstitial spaces within thecharge for adequate catalyst distribution within the digestingcellulosic biomass solids. Suitable techniques for using fluid flow todistribute a slurry catalyst within cellulosic biomass solids in such amanner are described in commonly owned U.S. Patent ApplicationPublication Nos. US20140005445 and US20140005444, which are incorporatedherein by reference in its entirety. In addition to affectingdistribution of the slurry catalyst, upwardly directed fluid flow maypromote expansion of the cellulosic biomass solids and disfavorgravity-induced compaction that occurs during their addition anddigestion, particularly as the digestion process proceeds and theirstructural integrity decreases. Methods of effectively distributingmolecular hydrogen within cellulosic biomass solids during hydrothermaldigestion is further described in commonly owned U.S. Patent ApplicationPublication Nos. US20140174433 and US20140174432, which are incorporatedherein by reference in its entirety.

In another embodiment the hydrothermal hydrocatalytic digestion unit maybe configured as disclosed in a co-pending U.S. Application PublicationNo. US20140117276 which disclosure is hereby incorporated by reference.In the digestion zone, the size-reduced biomass is contacted with thedigestive solvent where the digestion reaction takes place. Thedigestive solvent must be effective to digest lignins. The digestivesolvent is typically a solvent mixture having a boiling point of atleast 40° C.

In some embodiments, at least a portion of oxygenated hydrocarbonsproduced in the hydrothermal hydrocatalytic reaction zone are recycledwithin the process and system to at least, in part, form the in situgenerated solvent, which is used in the biomass digestion process.Further, by controlling the rate of digestion of biomass to lowermolecular weight fragments in the hydrothermal hydrocatalytic reaction(e.g., hydrogenolysis process), hydrogenation reactions can be conductedalong with the hydrogenolysis reaction at temperatures ranging of from110° C., preferably from about 150° C. to less than 300° C., mostpreferably from about 240° C. to about 270° C. As a result the fuelforming potential of the biomass feedstock fed to the process can beincreased.

In various embodiments, the fluid phase digestion medium (liquiddigestive solvent) in which the hydrothermal digestion and catalyticreduction reaction (in the hydrothermal hydrocatalytic reaction zone)are conducted, may comprise an organic solvent and water. The liquiddigestive solvent mixture may have a normal boiling point (i.e., atatmospheric pressure) of at least 40° C., preferably at least 60° C.,more preferably at least 80° C. Although any organic solvent thatcontains some oxygen atoms may be used as a digestion solvent,particularly advantageous organic solvents are those that can bedirectly converted into fuel blends and other materials and hence do notrequire extensive separation from intermediate streams used in theproduction of biofuels, or co-product streams used as fuel or separatedand processed as chemical products. That is, particularly advantageousorganic solvents are those that may be co-processed along with thealcoholic or oxygenated components during downstream processingreactions into fuel blends and other materials. Suitable organicsolvents in this regard may include, for example, ethanol, ethyleneglycol, propylene glycol, glycerol, phenolics and any combinationthereof. In situ generated organic solvents are particularly desirablein this regard.

In some embodiments, the liquid phase digestive solvent may comprisebetween about 1% water and about 99% water. Although higher percentagesof water may be more favorable from an environmental standpoint, higherquantities of organic solvent may more effectively promote hydrothermaldigestion due to the organic solvent's greater propensity to solubilizecarbohydrates and promote catalytic reduction of the solublecarbohydrates. In some embodiments, the liquid phase digestive solventmay comprise about 90% or less water by weight. In other embodiments,the fluid phase digestion medium may comprise about 80% or less water byweight, or about 70% or less water by weight, or about 60% or less waterby weight, or about 50% or less water by weight, or about 40% or lesswater by weight, or about 30% or less water by weight, or about 20% orless water by weight, or about 10% or less water by weight, or about 5%or less water by weight.

In some embodiments, catalysts capable of activating molecular hydrogenhydrothermal hydrocatalytic catalysts, which are capable of activatingmolecular hydrogen (e.g., hydrogenolysis catalyst) and conducting acatalytic reduction reaction may comprise a metal such as, for example,Cr, Mo, W, Re, Mn, Cu, Cd, Fe, Co, Ni, Pt, Pd, Rh, Ru, Ir, Os, andalloys or any combination thereof, either alone or with promoters suchas Au, Ag, Cr, Zn, Mn, Sn, Bi, B, O, and alloys or any combinationthereof. In some embodiments, the catalysts and promoters may allow forhydrogenation and hydrogenolysis reactions to occur at the same time orin succession of one another. In some embodiments, such catalysts mayalso comprise a carbonaceous pyropolymer catalyst containing transitionmetals (e.g., Cr, Mo, W, Re, Mn, Cu, and Cd) or Group VIII metals (e.g.,Fe, Co, Ni, Pt, Pd, Rh, Ru, Ir, and Os). In some embodiments, theforegoing catalysts may be combined with an alkaline earth metal oxideor adhered to a catalytically active support. In some or otherembodiments, the catalyst may be deposited on a catalyst support thatmay not itself be catalytically active.

In some embodiments, the hydrothermal hydrocatalytic catalyst maycomprise a slurry catalyst. In some embodiments, the slurry catalyst maycomprise a poison-tolerant catalyst. As used herein the term“poison-tolerant catalyst” refers to a catalyst that is capable ofactivating molecular hydrogen without needing to be regenerated orreplaced due to low catalytic activity for at least about 12 hours ofcontinuous operation. Use of a poison-tolerant catalyst may beparticularly desirable when reacting soluble carbohydrates derived fromcellulosic biomass solids that have not had catalyst poisons removedtherefrom. Catalysts that are not poison tolerant may also be used toachieve a similar result, but they may need to be regenerated orreplaced more frequently than does a poison-tolerant catalyst.

In some embodiments, suitable poison-tolerant catalysts may include, forexample, sulfided catalysts. In some or other embodiments, nitridedcatalysts may be used as poison-tolerant catalysts. Sulfided catalystssuitable for activating molecular hydrogen and buffers suitable for usewith such catalysts are described in commonly owned U.S. PatentApplication Publication Nos. US2012/0317872, US2013/0109896,US2012/0317873, and US20140166221, each of which is incorporated hereinby reference in its entirety. Sulfiding may take place by treating thecatalyst with hydrogen sulfide or an alternative sulfiding agent,optionally while the catalyst is disposed on a solid support. In moreparticular embodiments, the poison-tolerant catalyst may comprise (a)sulfur and (b) Mo or W and (c) Co and/or Ni or mixtures thereof. The pHbuffering agent, may be suitable be an inorganic salt, particularlyalkali salts such as, for example, potassium hydroxide, sodiumhydroxide, and potassium carbonate or ammonia. In other embodiments,catalysts containing Pt or Pd may also be effective poison-tolerantcatalysts for use in the techniques described herein. When mediating insitu catalytic reduction reaction processes, sulfided catalysts may beparticularly well suited to form reaction products comprising asubstantial fraction of glycols (e.g., C₂-C₆ glycols) without producingexcessive amounts of the corresponding monohydric alcohols. Althoughpoison-tolerant catalysts, particularly sulfided catalysts, may be wellsuited for forming glycols from soluble carbohydrates, it is to berecognized that other types of catalysts, which may not necessarily bepoison-tolerant, may also be used to achieve a like result inalternative embodiments. As will be recognized by one having ordinaryskill in the art, various reaction parameters (e.g., temperature,pressure, catalyst composition, introduction of other components, andthe like) may be modified to favor the formation of a desired reactionproduct. Given the benefit of the present disclosure, one havingordinary skill in the art will be able to alter various reactionparameters to change the product distribution obtained from a particularcatalyst and set of reactants.

In some embodiments, slurry catalysts suitable for use in the methodsdescribed herein may be sulfided by dispersing a slurry catalyst in afluid phase and adding a sulfiding agent thereto. Suitable sulfidingagents may include, for example, organic sulfoxides (e.g., dimethylsulfoxide), hydrogen sulfide, salts of hydrogen sulfide (e.g., NaSH),and the like. In some embodiments, the slurry catalyst may beconcentrated in the fluid phase after sulfiding, and the concentratedslurry may then be distributed in the cellulosic biomass solids usingfluid flow. Illustrative techniques for catalyst sulfiding that may beused in conjunction with the methods described herein are described inU.S. Patent Application Publication No. US2010/0236988, and incorporatedherein by reference in its entirety.

In various embodiments, slurry catalysts used in conjunction with themethods described herein may have a particulate size of about 250microns or less. In some embodiments, the slurry catalyst may have aparticulate size of about 100 microns or less, or about 10 microns orless. In some embodiments, the minimum particulate size of the slurrycatalyst may be about 1 micron. In some embodiments, the slurry catalystmay comprise catalyst fines in the processes described herein.

Catalysts that are not particularly poison-tolerant may also be used inconjunction with the techniques described herein. Such catalysts mayinclude, for example, Ru, Pt, Pd, or compounds thereof disposed on asolid support such as, for example, Ru on titanium dioxide or Ru oncarbon. Although such catalysts may not have particular poisontolerance, they may be regenerable, such as through exposure of thecatalyst to water at elevated temperatures, which may be in either asubcritical state or a supercritical state.

In some embodiments, the catalysts used in conjunction with theprocesses described herein may be operable to generate molecularhydrogen. For example, in some embodiments, catalysts suitable foraqueous phase reforming (i.e., APR catalysts) may be used. Suitable APRcatalysts may include, for example, catalysts comprising Pt, Pd, Ru, Ni,Co, or other Group VIII metals alloyed or modified with Re, Mo, Sn, orother metals such as described in U.S. Patent Publication No.US2008/0300435, and incorporated herein by reference in its entirety.

As described above, one or more liquid phases may be present whendigesting cellulosic biomass solids. Particularly when cellulosicbiomass solids are fed continuously or semi-continuously to thehydrothermal (hydrocatalytic) digestion unit, digestion of thecellulosic biomass solids may produce multiple liquid phases in thehydrothermal digestion unit. The liquid phases may be immiscible withone another, or they may be at least partially miscible with oneanother. In some embodiments, the one or more liquid phases may comprisea phenolics liquid phase comprising lignin or a product formedtherefrom, an aqueous phase comprising the alcoholic component, a lightorganics phase, or any combination thereof. The alcoholic componentbeing produced from the cellulosic biomass solids may be partitionedbetween the one or more liquid phases, or the alcoholic component may belocated substantially in a single liquid phase. For example, thealcoholic component being produced from the cellulosic biomass solidsmay be located predominantly in an aqueous phase (e.g., an aqueous phasedigestion solvent), although minor amounts of the alcoholic componentmay be partitioned to the phenolics liquid phase or a light organicsphase. In various embodiments, the slurry catalyst may accumulate in thephenolics liquid phase as it forms, thereby complicating the return ofthe slurry catalyst to the cellulosic biomass solids in the mannerdescribed above. Alternative configurations for distributing slurrycatalyst particulates in the cellulosic biomass solids when excessivecatalyst accumulation in the phenolics liquid phase has occurred aredescribed hereinafter.

Accumulation of the slurry catalyst in the phenolics liquid phase may,in some embodiments, be addressed by conveying this phase and theaccumulated slurry catalyst therein to the same location where a fluidphase digestion medium is being contacted with cellulosic biomasssolids. The fluid phase digestion medium and the phenolics liquid phasemay be conveyed to the cellulosic biomass solids together or separately.Thusly, either the fluid phase digestion medium and/or the phenolicsliquid phase may motively return the slurry catalyst back to thecellulosic biomass solids such that continued stabilization of solublecarbohydrates may take place. In some embodiments, at least a portion ofthe lignin in the phenolics liquid phase may be depolymerized before orwhile conveying the phenolics liquid phase for redistribution of theslurry catalyst. At least partial depolymerization of the lignin in thephenolics liquid phase may reduce the viscosity of this phase and makeit easier to convey. Lignin depolymerization may take place chemicallyby hydrolyzing the lignin (e.g., with a base) or thermally by heatingthe lignin to a temperature of at least about 250° C. in the presence ofmolecular hydrogen and the slurry catalyst. Further details regardinglignin depolymerization and the use of viscosity monitoring as a meansof process control are described in commonly owned U.S. PatentApplication Publication No. US20140117275, which disclosure isincorporated herein by reference in its entirety.

In some embodiments, a phenolics liquid phase formed from the cellulosicbiomass solids may be further processed. Processing of the phenolicsliquid phase may facilitate the catalytic reduction reaction beingperformed to stabilize soluble carbohydrates. In addition, furtherprocessing of the phenolics liquid phase may be coupled with theproduction of glycols or dried monohydric alcohols for feeding to acondensation catalyst. Moreover, further processing of the phenolicsliquid phase may produce methanol and phenolic compounds fromdegradation of the lignin present in the cellulosic biomass solids,thereby increasing the overall weight percentage of the cellulosicbiomass solids that may be transformed into useful materials. Finally,further processing of the phenolics liquid phase may improve thelifetime of the slurry catalyst.

Various techniques for processing a phenolics liquid phase produced fromcellulosic biomass solids are described in commonly owned U.S. PatentApplication Publication Nos. US20140121419, US20140117277, whichdisclosures are incorporated herein by reference in its entirety. Asdescribed therein, in some embodiments, the viscosity of the phenolicsliquid phase may be reduced in order to facilitate conveyance orhandling of the phenolics liquid phase. As further described therein,deviscosification of the phenolics liquid phase may take place bychemically hydrolyzing the lignin and/or heating the phenolics liquidphase in the presence of molecular hydrogen (i.e., hydrotreating) todepolymerize at least a portion of the lignin present therein in thepresence of accumulated slurry catalyst. Deviscosification of thephenolics liquid phase may take place before or after separation of thephenolics liquid phase from one or more of the other liquid phasespresent, and thermal deviscosification may be coupled to the reaction orseries of reactions used to produce the alcoholic component from thecellulosic biomass solids. Moreover, after deviscosification of thephenolics liquid phase, the slurry catalyst may be removed therefrom.The catalyst may then be regenerated, returned to the cellulosic biomasssolids, or any combination thereof. In some embodiments, heating of thecellulosic biomass solids and the fluid phase digestion medium (liquiddigestive solvent) to form soluble carbohydrates and a phenolics liquidphase may take place while the cellulosic biomass solids are in apressurized state. As used herein, the term “pressurized state” refersto a pressure that is greater than atmospheric pressure (1 bar). Heatinga fluid phase digestion medium in a pressurized state may allow thenormal boiling point of the digestion solvent to be exceeded, therebyallowing the rate of hydrothermal digestion to be increased relative tolower temperature digestion processes. In some embodiments, heating thecellulosic biomass solids and the fluid phase digestion medium may takeplace at a pressure of at least about 30 bar. In some embodiments,heating the cellulosic biomass solids and the fluid phase digestionmedium may take place at a pressure of at least about 60 bar, or at apressure of at least about 90 bar. In some embodiments, heating thecellulosic biomass solids and the fluid phase digestion medium may takeplace at a pressure ranging between about 30 bar and about 430 bar. Insome embodiments, heating the cellulosic biomass solids and the fluidphase digestion medium may take place at a pressure ranging betweenabout 50 bar and about 330 bar, or at a pressure ranging between about70 bar and about 130 bar, or at a pressure ranging between about 30 barand about 130 bar. Reference herein to pressure(s) is to gaugepressure(s).

The digestion and hydrodeoxygenation of the biomass solid describedabove, produces a stable oxygenated hydrocarbon intermediate product,that have a viscosity of less than 100 centipoise (at 50° C.),preferably less than 40 centipoise, a diol content (e.g., glycols) of atleast 2 wt %, preferably of at least 5 wt %, less than 2 wt % of sugar,and less than 2 wt % acid (based on acetic acid equivalent), based onthe total stream composition, and at least 60% of carbon exists inmolecules having 9 carbon atoms or less. By the term “stable”, theproduct is stable enough to be stored for at least 30 days where theviscosity does not change more than 50% and the main components (top 10percent based on mass basis) does not change in concentration by morethan 10%.

Optionally, the stable oxygenated hydrocarbon intermediate product canbe vaporized to allow ash separation from the liquid product. Thevaporized stable oxygenated hydrocarbon can then be provided to the diolconversion zone described below.

It was found that contacting (and reacting) the oxygenated hydrocarbonintermediate containing diols with an acidic amorphous silica aluminacatalyst, preferably mildly acidic amorphous silica alumina catalyst, ata temperature in the range of 300° C. to 400° C. producingmonooxygenated stream prior to condensation reaction can reduce cokeformation on the catalyst during subsequent condensation reaction.

In the inventive process, at least a portion of the stable oxygenatedhydrocarbon intermediate product is contacted, in a diol conversionzone, 30, with an acidic amorphous silica alumina catalyst at atemperature in the range from 300° C. to 400° C., preferably 325° C. to375° C., thereby producing monooxygentaed stream 32 containing water andmonooxygenates having a boiling point of at least 40° C. The temperatureand pressure is at a range that optimizes diol conversion whileminimizing coke formation (by oligomerization or condensationreactions). The pressure range may be from ambient (atmospheric)pressure to slight partial pressure, for example, total pressure of upto about 200 psi. The reaction typically converts at least 25%,preferably at least 50%, most preferably at least 75% of diols initiallypresent. Typically, the weight hourly space velocity is in the range of0.2 to 5 for the monooxygenate formation step.

The acidic amorphous silica-alumina catalyst is a solid catalyst thatmay be prepared in a number of ways which are known in the art. Forexample, by precipitating alumina in a silica slurry, followed byfiring. Some other examples include precipitation of hydrous aluminaonto amorphous silica hydrogel, reacting a silica sol with an aluminasol, coprecipitation from sodium silicate/aluminum salt solution. Thesulfate and the sodium, which may be introduced with the aluminaprecursors and sulfuric acid, may be removed by washing. The resultingsilica alumina material can be shaped in various shapes, for example, byextruding, oil drop process, or pressing. To produce the acidicamorphous silica-alumina catalyst, the material is dried and calcined.The BET surface area of the catalyst is typically greater than 200 m²/g,preferably in the range of 300 m²/g to 500 m²/g. The total pore volumeis typically in the range of 0.7 to 1.0 cc/g measured using watermethod. Although described herein as amorphous, the silica aluminamaterials useful in embodiments described herein may contain a minoramount of crystalline alumina and/or aluminosilicate, depending on thesource of the alumina material used to prepare the precipitatedalumina-silica precursor, the amount of the alumina in thealumina-silica, as well as the calcination temperature. The ratio ofsilica to alumina may vary between 1:99 to 99:1, preferably 15:85 to96:4. In some embodiments, 15:85 to 65:35, preferably 15:85 to 30:70 forlow silica content solid amorphous silica-alumina catalyst, preferably35:65 to 55:45 for higher silica content solid amorphous silica-aluminacatalyst. In another embodiment, milder acidity amorphous silica toalumina catalyst, the ratio of silica to alumina may vary between 45:55to 96:4, more preferably 45:55 to 90:10. Solid acid amorphoussilica-alumina catalyst is available commercially, for example, fromCriterion Catalyst Co., such as X-600 catalyst series, X-503 catalyst,X-801 catalyst or from CRI Catalyst Company such as KL-7122 catalyst.

As used herein, the term “condensation reaction” will refer to achemical transformation in which two or more molecules are coupled withone another to form a carbon-carbon bond in a higher molecular weightcompound, usually accompanied by the loss of a small molecule such aswater or an alcohol. The term “condensation catalyst” will refer to acatalyst that facilitates, causes or accelerates such chemicaltransformation.

The monooxygenated stream can be condensed (in this instance referred toliquid condensation without chemical transformation) in a cooling zone,40, to liquid producing an aqueous phase and an organic phase. It hasbeen found that the process provides additional advantage that themonooxygenated stream can be readily phase separated into an aqueousphase and an organic phase upon condensation, thus allowing the aqueousphase containing water and a residual amount of unconvertedmonooxygenated compounds and diols of carbon number less than four, tobe readily removed from the organic phase enriched in monooxygenatedorganic compounds greater than carbon number four, and phenoliccompounds. This removal of the aqueous phase, 45, provides for anadditional advantage of removal of water from the process that reducethe degradation of the subsequent condensation catalyst and extendscatalyst life.

The separation of the aqueous phase and the organic phase can be bydecanting, liquid-liquid extraction, centrifugation, or use ofhydroclones or other devices using the density differences betweenimmiscible phases as the basis for separation. Distillation may also beused for a process where the digestion and hydrodeoxygenation step hasbeen optimized to produce mainly diols and higher molecular weightmonooxygenations, such that water with only a small amount ofmonooxygenates less than C4 are present as the aqueous misciblecomponent.

Further, the organic phase may provide a good digestive solvent.Optionally, at least a first portion of the organic phase(monooxygenates having a boiling point of at least 40° C.) may berecycled via a recycle stream (recycle line), 47, to the hydrothermalcatalytic reaction zone (digestion and hydrodeoxygenation) as a portionof the digestive solvent. It has been found that the monooxygenatestream produced by the diol conversion zone after removal of water maybe a good digestive solvent for the digestion and hydrodeoxygenation ofthe biomass solid. Such stream contains minimal water and containsmonooxygenates that can be converted to biofuel components in thesubsequent condensation reaction step(s).

At least a second portion of the organic phase (containing themonooxygenates) having boiling point of at least 40° C. is contacted, ina condensation reaction zone, 50, with a strong acidic solid catalyst ata temperature in the range from 300° C. to about 350° C. and a pressurein a range from 500 psi to 1200 psi, preferably from 600 psi to 1000psi, to produce a higher hydrocarbons stream containing unsaturatedhydrocarbons including olefins and dienes. The strong acidic solidcatalyst may include, for example, mineral based acidic catalyst such asacidic clay, acidic silica alumina, and acidic zeolites such as H-ZSM-5,and Mordenite as long as the temperature is maintained below about 350°C. Reference herein to pressure(s) is to gauge pressure(s).

The condensation reaction mediated by the condensation catalyst may becarried out in any reactor of suitable design, includingcontinuous-flow, batch, semi-batch or multi-system reactors, withoutlimitation as to design, size, geometry, flow rates, and the like. Thereactor system may also use a fluidized catalytic bed system, a swingbed system, fixed bed system, a moving bed system, or a combination ofthe above. In some embodiments, bi-phasic (e.g., liquid-liquid) andtri-phasic (e.g., liquid-liquid-solid) reactors may be used to carry outthe condensation reaction.

The condensation product 52, may be low aromatics,paraffinics-containing stream. The low aromatics, paraffinic-containingstream may be further treated in a hydrotreating step (hydrotreatingzone, 70) to produce biofuel useful as diesel, 75. This step can be anyconventional hydrotreating process. This includes fixed or ebulated bedoperations at conventional operating conditions such as temperatures inthe range of 250° C. to 450° C., preferably 300° C. to 380° C. Pressuresare also conventional such as 20-70 bar of hydrogen. Catalysts used inthe hydrotreating step are preferably those employed conventionally,such as mixed cobalt and/or nickel and molybdenum sulfides supported onalumina and mixed nickel and tungsten sulfides supported on alumina orsilica. The combined process of this invention will also benefit newlydeveloped catalysts such as those containing ruthenium sulfide andcatalysts using novel supports such as silica-aluminas, carbons or othermaterials. For details on the state of the art in conventionalhydrotreating processes, we refer to “Hydrotreating Catalysis-Scienceand Technology”, by H. Topsøe, B. S. Clausen and F. E. Massoth,Springer-Verlag Publishers, Heidelberg, 1996.

The hydrotreated higher hydrocarbon stream contains aliphatichydrocarbons. The product will have less unsaturates such as olefins anddienes after hydrotreating.

To facilitate a better understanding of the present invention, thefollowing examples of preferred embodiments are given. In no way shouldthe following examples be read to limit, or to define, the scope of theinvention.

ILLUSTRATIVE EXAMPLES Example 1

Digestion and Hydrodeoxygenation of Lignocellulosic Biomass To screenfor reaction selectivity in digestion of biomass, a 50-milliliter Parr4590 reactor was charged with 6.01 grams of tetrahydrofuran and 17.99grams of deionized water solvent, together with 0.099 grams of potassiumhydroxide, and 0.1075 grams of Raney™ cobalt catalyst (from WR Grace2724).

The reactor was then charged with 1.99 grams of southern pine mini-chips(10% moisture), of nominal size 3×5×5 mm in dimension, before pressuringwith 52 bar of hydrogen, and heating with stirring to 190° C. for 1hour, followed by heating to 240° C. for 4 hours. At the end of the5-hour reaction cycle, the reactor was cooled, and allowed to gravitysettle overnight.

The reaction cycle was repeated three times via addition of 2 more gramsof wood chips, and re-pressuring with 52 bar of H₂ before heating usingthe same temperature profile.

After four cycles, the reactor product was analyzed by gaschromatography using a 60-m×0.32 mm ID DB-5 column of 1 micrometerthickness, with 50:1 split ratio, 2 ml/min helium flow, and column ovenat 40° C. for 8 minutes, followed by ramp to 285° C. at 10° C./min, anda hold time of 53.5 minutes. The injector temperature was set at 250°C., and the detector temperature was set at 300° C. A range of alkanes,ketone and aldehyde monooxygenates as well as glycol intermediatesincluding ethylene glycol (EG), 1,2-propylene glycol (PG) and glycerolwere observed. Total products observed in the gas chromatographicanalysis summed to about 30% of the maximum expected yield if allcarbohydrates were converted to mono-oxygenated or diol products.Ethylene glycol (EG) formation, and 1,2-propylene glycol (PG) formationcomprised approximately 20% of observed products. All observed reactionproducts exhibited volatility greater than C6 sugar alcohol sorbitol.

Examples 2 and 3: Digestion and Hydrodeoxygenation of LignocellulosicBiomass

Example 1 was repeated with use of 0.3083 (Example 2) and 0.4051(Example 3) grams of Raney Cobalt catalyst. For example 2, the amount ofethylene glycol formed increased to 1.49 weight percent, and1,2-propylene glycol formation increased to 1.65 weight percent Total GCobservable products increased to 10.5 wt. %, or 96% of the expectedproduct formation from selective conversion of carbohydrates present inwood feed. Glycols EG and PG comprised about 29% of observed products.

For example 3 with 0.4051 grams of Raney Cobalt catalyst, 1.4 wt. %ethylene glycol was formed, together with 1.64 wt. % of 1,2-propyleneglycol. Observed yields were estimated as 99% of those expected fromcomplete conversion of carbohydrates in wood feed, while ethylene glycoland 1,2-propylene glycol comprised about 28% of observed products.

These examples show formation of diols ethylene glycol and 1,2-propyleneglycol via simultaneous digestion and hydrotreating reaction of woodybiomass, in the presence of hydrogen and a metal catalyst capable ofactivating molecular hydrogen. The diols were the largest singlecomponents observed in gas chromatographic analysis of product. Yieldswere increased by increasing the catalyst concentration, to increase therate of hydrotreating and stabilization of intermediates derived fromthe hydrothermal digestion of woody biomass.

Example 4: Digestion and Hydrodeoxygenation of Lignocellulosic

A 75-ml Parr5000 reactor was charged with 6.04 grams of 2,6-dimethylphenol (xylenol), 18.06 grams of deionized water, 0.207 grams of amixture of 860 ppm dimethylsulfoxide in deionized water, 0.085 grams ofpotassium hydroxide buffer, and 0.45 grams of nickel-oxide promotedcobalt molybdate catalyst (DC-2534, containing 1-10% cobalt oxide andmolybdenum trioxide (up to 30 wt. %) on alumina, and less than 2%nickel), obtained from Criterion Catalyst & Technologies L.P., andsulfided by the method described in US2010/0236988 Example 5.

The reactor was then charged with 2.07 grams of southern pine mini-chips(10% moisture), of nominal size 3×5×5 mm in dimension, before pressuringwith 40 bar of hydrogen, and heating to 200° C. for 1 hours, thenramping to 255° C. for 1.5 hours.

GC analysis of final liquid revealed 1.63 wt. % ethylene glycol and 1.60wt. % propylene glycol, for a yield of more than 30% of the GC-measuredproducts derived from carbohydrates.

Example 5: Sulfided Cobalt Molybdate Catalyst at Higher Temperature

Example 4 was repeated with a heating cycle of 1 hour at 200° C.followed by 1.5 hours at 265° C. Observed ethylene glycol and propyleneglycol produced was 1.01 and 1.08 wt. % respectively, with the highertemperature end condition.

Examples 6 & 7: Digestion and Hydrodeoxygenation of LignocellulosicBiomass

For Example 6, the experiment of Example 4 was repeated with a solventmixture of 12.5% cresol in deionized water, and a heating cycle of 1hour at 190° C. followed by 4 hours at 240° C. GC analysis indicated ayield of ethylene glycol (EG) and 1,2-propylene glycol (PG)corresponding to 6.75% of total carbohydrates charged, with ethyleneglycol comprising 36% of these total of these diols. Wood digestion wascomplete, and more than 100 components with retention time less thansorbitol were detected in the GC analysis.

For Example 7, the experiment of Example 6 was repeated with addition of1.8 grams of 99% purity cellulosic floc, instead of pine wood. Yield ofEG and PG was calculated as 8.5% of the total carbohydrate charged.

Examples 8 & 9: Digestion and Hydrodeoxygenation of LignocellulosicBiomass

Experiment 6 was repeated with use of 0.251 grams of 5% Platinum/aluminaas catalyst (STREM Chemicals). The reactor was again heated for 1 hourat 190° C. followed by 4 hours at 240° C. Yield of diols EG and PG was4.78% of the carbohydrate charged to the reactor.

Experiment 7 was repeated with 0.248 grams of the 5% Pt/alumina catalystas reaction catalyst. Yields of diols EG and PG were calculated as 5.26%of the total carbohydrate charged to the reactor as cellulosic floc.

Experiments 6-9 conducted under otherwise identical conditions, showsubstantial formation of diols as products, among a large number ofcomponents formed with boiling points less than sorbitol. Yields ofdiols EG and PG were higher with the sulfided cobalt molybdate catalyst,than for the supported platinum catalyst, under the conditions tested.

Example 10: Generation of Digester/Hydrodeoxygenation Intermediate

A 2-Liter Parr reactor with was charged with 1000.5 grams of deionizedwater solvent, 0.401 grams of potassium hydroxide buffer, and 29.8 gramsof Raney Cobalt 2724 catalyst (WR Grace). 66.7 grams of southern pinewood at nominal 10% moisture were added for reaction cycles conductedunder 52 bar of H₂, with heating to 160° C. for 1 hour, followed by 190°C. for 1 hour, followed by 240° C. for 3 hours.

Six cycles of wood addition were completed, with KOH buffer added at1.5-2.0 grams per cycle, to maintain pH greater than 4.5. After 6cycles, 250 grams of toluene were added (Sigma-Aldrich HPLC grade), andthe reactor was stirred for one hour at 150° C. to extract. Stirring wasstopped, the reactor was cooled, vented, and opened for removal ofliquid phases.

44.2 grams of organic upper layer, and 1019 grams of aqueous lower layerwere decanted via suction. The remaining wood residue and catalyst weredissolved in 250 grams of acetone solvent, for analysis by gaschromatography.

A sample of the aqueous layer product was analyzed by gas chromatographyusing a 60-m×0.32 mm ID DB-5 column of 1 μm thickness, with 50:1 splitratio, 2 ml/min helium flow, and column oven at 40° C. for 8 minutes,followed by ramp to 285° C. at 10° C./min, and a hold time of 53.5minutes. The injector temperature was set at 250° C., and the detectortemperature was set at 300° C. Gas Chromatographic-Mass Spec (GCMS) waseffected using the same protocol.

Principal products were ethylene glycol, 1,2-proplene glycol, along withlight monooxygenates C1-C3, intermediate C4-C6 monooxygenates (ketones,alcohols) and diols. Several phenolic components were formed(methoxypropylphenol, propylphenol) and extracted via toluene into theupper organic layer.

Example 11: Distillation of Aqueous Product from Reaction

771.6 grams of the aqueous intermediate product from Example 10 and 8.1grams of ceramic boiling chips were charged to a 2-liter 24/40 3-neckflask equipped with a short path Vigreux column (approximately 4stages). The flask was brought to a boil under a nominal atmosphere ofnitrogen, and 702.5 grams of a water-rich cut were removed. Vacuum wasapplied (approximately 50-100 Torr), and 77.9 grams of a middle boilingcut were removed as the bottoms kettle temperature was ramped from 100to 350° C. Maximum tops temperature was 150° C. A bottoms residue of13.1 grams was obtained, for a mass balance closure of 98.8%.

The middle boiling second distillate fraction was analyzed by GC-massspec, to reveal the composition shown in Table 1 below. A large numberof diol intermediates were formed.

Example 12: Diol Conversion

Feed: Fraction 2 from Example 11 was diluted 1/1 with DI water 7.5 g ofASA X600 (amorphous silica alumina trilobe extrudate from CriterionCatalyst Co., LP, 55% alumina (Al₂O₃), 45% silica (SiO₂)) was charged toa 10 inch reactor and heated to 350° C. under flowing nitrogen (50cc/min, 130 psig reactor pressure). Feed was introduced at 7.2 g/hr. 85g of liquid product was collected of which 7 g was organic phase whilethe remainder comprised an aqueous phase.

A table of compiled GCMS data from Examples 11 and 12 above is providedbelow. Other is C5-C6 higher oxygenates such as triols etc.

TABLE 1 Digestion/Hydrodoxygenation liquor mono-ol diol ketone cyclicether lactone other 9.62 48.52 3.69 3.73 3.11 31.33 ASA product olefindiene cyclic ether ketones aldehyde aromatic 17.70 9.49 20.42 19.2019.28 14.59As can be seen from the table above, diols were below detection limitafter diol conversion reaction with ASA.

The GC/MS of the feed after digestion and hydrodeoxygention from Example11 is shown in FIG. 2. The GC/MS of the diol conversion product fromExample 12 is shown in FIG. 3.

Example 13: Diols Conversion

A model feed mixture was prepared withPG/EG/butanediol/pentanediol/water feed (wt % 3.75/3.75/3.75/3.75/85),and charged to a ½ inch OD continuous flow reactor containing 7.6856 gASA X600 (amorphous silica alumina from Criterion Catalyst Co., LP, 55%alumina (Al₂O₃), 45% silica (SiO₂)) at 350° C. and 7.6 barg withnitrogen flow at 50 cc/min WHSV 1.56 g/g on total feed basis, (0.23 g/gon organic basis). The products from this reaction was condensed atambient temperature and pressure. Product from this reaction was approx1% organic and 99% aqueous. The organic phase had no remainingdetectable diols by GC-MS. The organic phase contained 33-68 wt %monooxygenates including cyclic ethers such as tetrahydro pyrane, methyltetrahydrofuran and aldehydes such as pentanal and butanal, propanal andacetone and 3 wt % olefins and dienes, substituted aromatics and higherhydrocarbons in the range of C5-C12.

Example 14: Condensation Reaction of Example 13

The organic phase from Example 13 was decanted from the aqueous phaseand charged to a second ¼ inch OD flow reactor equipped with a 2 mLinjection port to allow small samples to be charged in plugged flow.Reactor conditions were 0.5580 g ASA X600 (amorphous silica alumina fromCriterion Catalyst Co., LP, 55% alumina (Al₂O₃), 45% silica (SiO₂)), at350° C., 52 barg with 75 ccmin of flowing N₂. WHSV 3.2 g/g based ontotal flow (organic only). Product from this reaction was 14% organiclayer, remainder aqueous. The organic product contained less than 21percent monooxygenates and primarily higher hydrocarbons such asC10-C16. This product may be hydrotreated to produce a product useful asdiesel fuel.

Gas Chromatograph of the condensation product compared with a commercialNo. 2 standard diesel is provided in FIG. 4 and FIG. 5. For the gaschromatography, one microliter sample of the intermediate was injectedinto a GC insert held at 250° C., followed by Restek RTX-1701 (60 m) andDB-5 (60 m (capillary GC columns in series (120 m total length, 0.32 mmID, 0.25 μm film thickness) for an Agilent/HP 6890 GC equipped flameionization detector. Helium flow was 2.0 mL/min (constant flow mode),with a 10:1 split ratio. The oven temperature was held at 35° C. for 10min, followed by a ramp to 270° C. at 3 C/min, followed by a 1.67 minutehold time. The detector temperature was held at 300° C.

We claim:
 1. A process for the production of a higher hydrocarbon fromsolid biomass, said process comprising: a. providing a biomass solidcontaining cellulose, hemicellulose, and lignin; b. digesting andhydrodeoxygenating the biomass solid in a liquid digestive solvent, saidliquid digestive solvent containing a solvent mixture having a boilingpoint of at least 40° C., in the presence of a hydrothermalhydrocatalytic catalyst and hydrogen at a temperature in a range of from110° C. to less than 300° C. and at a pressure in a range of from 20 barto 200 bar to form a stable oxygenated hydrocarbon intermediate producthaving a viscosity of less than 100 centipoise (at 50° C.), a diolcontent of at least 2 wt %, less than 2 wt % of sugar, and less than 2wt % acid (based on acetic acid equivalent), based on the stableoxygenated hydrocarbon intermediate product, and at least 60% of carbonin the stable oxygenated hydrocarbon intermediate product exists inmolecules having 9 carbon atoms or less; c. reacting at least a portionof the stable oxygenated hydrocarbon intermediate product with an acidicamorphous silica alumina catalyst at a temperature in a range from 300°C. to 400° C. to convert diol in the stable oxygenated hydrocarbonintermediate product into monooxygenates compounds thereby producingmonooxygenated stream containing water and monooxygenates having aboiling point of at least 40° C.; d. condensing the monooxygenatedstream thereby producing an aqueous phase and an organic liquid phase;e. removing at least a portion of the aqueous phase from the organicliquid phase to provide a condensed organic stream containing themonooxygenates; and f. contacting monooxygenates having boiling point ofat least 40° C. in the condensed organic stream with a strong acidicsolid at a temperature in a range from 300° C. to about 350° C. and apressure in a range from 500 to 1200 psi thereby producing a higherhydrocarbons stream containing unsaturated hydrocarbons includingolefins and dienes.
 2. The process of claim 1 wherein a fraction of diolconverted in the step c is at least 25%.
 3. The process of claim 2wherein the fraction of diol converted in the step c is at least 50%. 4.The process of claim 3 wherein the fraction of diol converted in thestep c is at least 75%.
 5. The process of claim 1 wherein the step b iscarried out at a temperature in a range of 150° C. to 30° C.
 6. Theprocess of claim 1 wherein the acidic amorphous silica alumina catalysthas a BET surface area of greater than 200 m²/g.
 7. The process of claim1 wherein the hydrothermal hydrocatalytic catalyst is a heterogeneouscatalyst.
 8. The process of claim 1 wherein the solid biomass is alignocellulosic biomass.
 9. The process of claim 1 wherein the higherhydrocarbons stream is hydrotreated thereby producing a hydrocarbonsstream containing aliphatic hydrocarbons.
 10. The process of claim 2wherein the higher hydrocarbons stream is hydrotreated thereby producinga hydrocarbons stream containing aliphatic hydrocarbons.
 11. The processof claim 3 wherein the higher hydrocarbons stream is hydrotreatedthereby producing a hydrocarbons stream containing aliphatichydrocarbons.
 12. The process of claim 6 wherein the higher hydrocarbonsstream is hydrotreated thereby producing a hydrocarbons streamcontaining aliphatic hydrocarbons.
 13. The process of claim 1 wherein areaction pressure in the step c is in a range of from atmosphericpressure to about 200 psi.
 14. The process of claim 13 wherein thehigher hydrocarbons stream is hydrotreated thereby producing ahydrocarbons stream containing aliphatic hydrocarbons.